CN106753559A - A kind of method of dry gas producing ethylene cracking material through hydrogenation - Google Patents
A kind of method of dry gas producing ethylene cracking material through hydrogenation Download PDFInfo
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Abstract
The invention discloses a kind of method of dry gas producing ethylene cracking material through hydrogenation.Dry gas containing alkene, optional hydrogen make-up, cocurrent enter fixed bed hydrogenation reactor, are contacted with hydrogenation catalyst under hydrogenation process conditions and are reacted, and gained product is by obtaining the dry gas of alkene saturation after separation；Wherein include more than two conversion zones in hydrogenation reactor, according to the engagement sequence with material, activity of the activity of hydrogenation catalyst higher than hydrogenation catalyst in upstream reaction section in downstream reaction section.The inventive method can control the speed of olefin hydrogenation, olefin hydrogenation conversion ratio is set smoothly to be stepped up along beds, reaction heat is able to progressively gentle releasing, released rather than concentrating, reduce the reaction temperature rising of beds, " thermometer bulb " of beds is greatly gentle, so as to extend the service life of catalyst.
Description
Technical field
The present invention relates to a kind of low-carbon alkene hydroprocessing technique.Specifically, it is a kind of method by olefin-containing dry gas producing ethylene cracking material through hydrogenation.
Background technology
At present, raw material that China's ethylene unit is used is more based on naphtha (naphtha account for 64%, hydrogenation tail oil account for 10%, light diesel fuel account for 10%), ethylene raw is the main factor for influenceing thylene cost, and raw material proportion in totle drilling cost is 70%~75%, even more high.In recent years, Domestic Petrochemical Enterprises were newly-built, extended many large-scale ethylene producing devices of set, although raw material sources, but ethylene cracking material or pretty nervous have been widened in actual production；In addition, crude oil price rises steadily, ethylene cracking material naphtha price is also increased, and ethylene producing device economy is deteriorated.Realistic situation forces enterprise to find new ethylene raw to solve this problem, C2~C5Cut fraction hydrogenation is exactly one of the effective ways for solving this problem as ethylene raw.
At present, domestic many walks the petroleum chemical enterprise of Integrated Refinery And Petrochemical, existing ethylene unit, while also there is the coking dry gas of affluence.And ethane and a small amount of ethene are rich in coking dry gas, if wherein a small amount of ethene is carried out into saturated hydrogenation, this coking dry gas is exactly good ethylene raw.
Under normal conditions, industrial C2Olefin(e) centent in cut is higher, while also containing the impurity such as a small amount of sulphur.Such as by C2Cut directly as preparing ethylene by steam cracking raw material, alkene can occur in pyrolysis furnace polymerization, cyclisation, condensation and coking reaction.Therefore, it is necessary to hydrogenation of olefins is made into alkane.
Hydrogenation of olefins in coking dry gas is transformed into alkane, is in theory simple and easy to apply, but many difficult points are had in the specific implementation process of technology.Such as, coking dry gas composition has following features：（1）Contain carbon monoxide and carbon dioxide；（2）Sulfur-bearing is higher；（3）While to coking dry gas hydrogenation, hydrogenation depth deoxidation is also wanted, and to reach oxygen content index ≯ 1.0mg. m-3；（4）Coking dry gas key component is C2, thermal capacitance value is relatively low；Exothermic heat of reaction is concentrated, hot(test)-spot temperature（Or thermometer bulb）It is too high.
CN1800308A discloses a kind of dry-gas recovery C2And C2The method of above hydrocarbon component.The method includes following processing routine to dry gas：More than ten operation such as pressure-variable adsorption, amine wash-out sulphur, washing, water separation, fine de-sulfur, dearsenification, fine de-sulfur, deoxidation, alkali cleaning carbon dioxide removal, washing dealkalize, water separation, dealkalize, Adsorbing drying by pressure variation.Although tissue production in this way can obtain ethylene cracking material, production procedure is oversize, and cumbersome, production cost is higher.
For problem present in the above method, CN103450941A is improved, it is proposed that a kind of method that coking dry gas prepare ethylene cracking material.The method uses sulfide type catalyst, to coking dry gas using following processing routine successively：（1）Amine is carried out to coking dry gas to wash；Slough H2S、CO2, coke powder.（2）Coking dry gas are hydrogenated with, deolefination, deoxidation, removing part CO and CO2.（3）Coking dry gas are carried out with pressure-variable adsorption, rich ethane gas is collected.Three in aforementioned four difficult point are solved, while compared with CN1800308A ratios, flow is also simplify, but exothermic heat of reaction is concentrated, hot(test)-spot temperature（Or thermometer bulb）Too high problem still fails to solve.
In addition, each enterprise produces, dry gas composition difference is larger, and the alkene and oxygen content that generally major part enterprise is produced in dry gas are in moderate quatity, i.e. olefin(e) centent 4% ~ 9%, and oxygen content is in 600 ~ 1200 mg m-3, this dry gas hydrogenation reaction it is important that deoxidation aspect and deolefination lay equal stress on, if produced according further to CN103450941A, product is extremely difficult to index.
The content of the invention
For the deficiency of above-mentioned method of hydrotreating, the present invention develops a kind of improved olefin-containing dry gas method of hydrotreating.The method can control the speed of olefin hydrogenation, olefin hydrogenation conversion ratio is set smoothly to be stepped up along beds, reaction heat is able to progressively gentle releasing, released rather than concentrating, reduce the reaction temperature rising of beds, " thermometer bulb " of beds is greatly gentle, so as to extend the service life of catalyst.
Present inventor, by carrying out system research to coking dry gas hydrogenation reaction of the prior art, obtains following understanding：
（1）This reaction is gas phase and strong exothermal reaction, and example is typically consisted of with the enterprise's coking dry gas of table 1, and its reaction is 6.55 for the thermal discharge of the coking dry gas raw material hydrogenation reaction of 1mol
KJ·mol-1；Preferable adiabatic temperature rise is 80 DEG C.
Table
1
Enterprise's coking dry gas are typically constituted
（2）This reaction is reacted for one-level flash hydrogcnation, in olefines hydrogenation reaction, C2Alkene is most easily to be hydrogenated with, and is also most fast reaction speed.
（3）Exothermic heat of reaction is very uneven；Reaction is using top charging, bottom discharging, the interior beds equal including four admission spaces of reactor.According to Flow of Goods and Materials direction, the conversion ratio highest of beds first paragraph, the 80% of up to 80%, i.e. total reaction heat releases in beds first paragraph；The conversion ratio that the 4th section of beds is minimum, and generally only 2%.If representing the reaction speed in differential responses section with the conversion ratio of the conversion ratio of relatively average reaction speed=certain section/another section, then the relatively average reaction speed of the first conversion zone is most fast, the average response speed of the second conversion zone, the average response speed of the 3rd conversion zone is slower, and the average response speed of the 4th conversion zone section is most slow.
Because the hydrogenation activity of hydrogenation catalyst is and the hydrogenation active metals content of catalyst into positive correlation, so, in order to control the speed of olefin hydrogenation, olefin hydrogenation conversion ratio is set smoothly to be stepped up along beds, reaction heat is able to progressively gentle releasing, released rather than concentrating, it should the method that grading loading is used to catalyst：The catalyst for being loaded is that the hydrogenation active metals content of first paragraph catalyst is minimum, final stage should highest.From first paragraph to the 4th section, the hydrogenation active metals content of catalyst should increase successively by a certain percentage.
Above-mentioned result of study is to our enlightenment：（1）The hydrogenation depth for walking reactions steps from surface to control this to react.I.e. we can be according to C2The characteristics of olefin hydrogenation, the method matched somebody with somebody using level to catalyst：I.e. along the direction of Flow of Goods and Materials, the hydrogenation activity of institute's loading catalyst is stepped up, and hydrogenation reaction depth is steadily stepped up along the direction of Flow of Goods and Materials, and reaction heat is also steadily to release step by step.
Based on above-mentioned discovery, present inventor proposes a kind of method of dry gas producing ethylene cracking material through hydrogenation, including herein below：
Dry gas containing alkene, optional hydrogen make-up, cocurrent enter fixed bed hydrogenation reactor, are contacted with hydrogenation catalyst under hydrogenation process conditions and are reacted, and gained product is by obtaining the dry gas of alkene saturation after separation；
Wherein include more than two conversion zones in hydrogenation reactor, according to the engagement sequence with material, activity of the activity of hydrogenation catalyst higher than hydrogenation catalyst in upstream reaction section in downstream reaction section.
In the method for the present invention, the activity of hydrogenation catalyst is represented with the height of contained active metal component content in catalyst.
Hydrogenation catalyst used in the inventive method, can select conventional hydrogenation catalyst in the art.Described hydrogenation catalyst can be load hydrogenation catalyst or body phase hydrogenation catalyst.Load hydrogenation catalyst includes the active metal component of carrier and load.The carrier is generally porous refractory inorganic oxide or activated carbon.Specifically, carrier is generally selected from Al2O3, containing SiO2Al2O3、TiO2, the Al containing molecular sieve2O3With one or more in one group of material of activated carbon composition.Active metal component is selected from base metal, is such as generally selected from one or more in W, Mo, Ni and Co.In the present invention, base metal preferably includes W and/or Ni.In terms of metal oxide, the content of non-noble metal components is generally 5 wt%~35
wt%。
Body phase hydrogenation catalyst contains tri- kinds of metal components of Mo, W, Ni, and wherein W, Ni exists with composite oxides form：NixWyOz, z=x+3y, Mo exist with oxide form：MoO3.Composite oxides NixWyOzThe ratio (atomic molar ratio) of middle x and y is 1: 8~8: 1, preferably 1: 4~4: 1.Composite oxides NixWyOzWith oxide M oO3Weight ratio be 1: 10~10: 1, preferably 1: 5~5: 1.Composite oxides Ni in bulk phase catalystxWyOzWith oxide M oO3Gross weight content be 40%~100%, preferably 50%~8%.（Composition when above-mentioned catalyst composition is for oxidation state, catalyst needs to carry out vulcanizing treatment by method well known to those skilled in the art when in use）.
According to the engagement sequence with reaction mass, the content of active metal component is usual than active metal component in hydrogenation catalyst in adjacent upstream reaction section in hydrogenation catalyst in downstream reaction section（In terms of metal oxide）Content 2~30 percentage high, 3~20 percentage preferably high.
In the method for the present invention, the number of conversion zone preferably 3~5 in hydrogenation reactor.The volume of the hydrogenation catalyst of filling can be with equal or different in each conversion zone.
When 4 conversion zones are included in reactor, according to the engagement sequence with reaction mass, the first conversion zone, the second conversion zone, the 3rd conversion zone and the active metal component in the 4th conversion zone in hydrogenation catalyst（In terms of oxide）Weight content typically be respectively 5%~20%, 10%~25%, 15%~30%, 20%~50%, active metal component in catalyst in adjacent conversion zone（In terms of oxide）Content differ 2~30 percentages, preferably 3~20 percentages.
The described dry gas raw material containing alkene is selected generally from coking dry gas, catalytic cracked dry gas, thermal cracking dry gas, is hydrocracked the gas of the oil plant institute by-product of rich gas, catalytic reforming gas, or similar composition；The dry gas is rich in C2C can also be contained while cut3Cut, C4Cut.Alkene in olefin-containing dry gas is mainly C2Alkene, it is possibility to have a small amount of C3Alkene or C4Alkene, wherein alkene（Generally ethylene contents account for more than 80%, and surplus alkene is C3~C4Alkene）Volume fraction be generally more than 1.0v%, most preferably preferably more than 2.0v%, 4.0v%~9.0v%.Meanwhile, the oxygen content in raw material dry gas is generally 100
mg·m-3More than, preferably 300 mgm-3~1200 mgm-3。
In the method for the present invention, typically hydrogen is also contained simultaneously in the dry gas raw material of olefin-containing.The volume fraction of hydrogen is generally 2 more than v%, preferably 5.0 more than v%, most preferably 5.0 v%~10.0 v% in olefin-containing dry gas.Under normal conditions, the ratio between molar fraction of molar fraction of hydrogen and alkene will be more than 1.0 in the dry gas of olefin-containing；If during hydrogen deficient, can toward a small amount of hydrogen make-up is mixed in olefin-containing dry gas, to meet olefin hydrogenation the need for.
In the method for the present invention, the implication of " the optional hydrogen make-up " refers to that hydrogen make-up is not essential.When the amounts of hydrogen contained in olefin-containing dry gas disclosure satisfy that the need for hydrogenation of olefins, hydrogen make-up can not be included in charging；Need to include the hydrogen of supplement when the hydrogen content in dry gas is insufficient for the need for hydrogenation of olefins, in charging.
Applicant also found when studying olefin hydrogenation dynamics：Olefin hydrogenation is gas（Coking dry gas）Gu-（Catalyst）Reaction；Rate-determining steps are catalyst surface reactions steps, and the reaction mechanism mechanism of reaction includes following five step：①、C2Olefin component is diffused into catalyst surface（Outer surface, inner surface）；②、C2Olefin component is adsorbed on hydrogenation sites；③、C2Olefin component completes hydrogenation reaction；④、C2Alkane component is desorbed from hydrogenation sites；⑤、C2Alkane component is diffused into product from catalyst surface.
Above-mentioned result of study is to our enlightenment：If we can adopt a kind of means, increase the reactions steps of reaction mass transfer, increased the mass transfer step of external diffusion, change original coking dry gas hydrogenation reaction course, reaction speed is controlled with this, the releasing of delayed response heat equally enables to reaction bed temperature than more uniform, reaction temperature rising reduces, and " thermometer bulb " of beds is greatly gentle.
Therefore, in the method for the invention, except carrying out level with outer using the hydrogenation catalyst of different activities, while the dry gas of olefin-containing feeds, can also be while toward one distillate of introducing in reactor.
Alkadienes is free of in introduced distillate, it can contain a small amount of monoolefine, the content of contained monoolefine is not higher than 4.0 wt%.
The distillate introduced in reaction will ensure at reaction conditions at least partly in liquid.Described distillate can be refined naphtha, non-aromatic gasoline, hydrofinishing aviation kerosine, hydrogenated diesel oil, or at reaction conditions in other distillates of liquid；Alkadienes cannot be contained in distillate, contained monoolefine is not more than 4.0
wt%.The initial boiling point of described distillate is typically higher than 50 DEG C, preferably more than 60 DEG C；The end point of distillation of distillate is generally less than 400 DEG C, preferably less than 360 DEG C.
In the method for the present invention, described hydrogenation process conditions include：Reaction pressure is 0.5~6.0MPa, preferably 1.5~4.0MPa；Reaction inlet temperature is 120 DEG C~300 DEG C, preferably 140 DEG C~280 DEG C；Reaction outlet temperature is generally 130 DEG C~400 DEG C, preferably 220 DEG C~360 DEG C；The volume space velocity of olefin-containing dry gas is 100~10000 h-1, preferably 300~5000 h-1.The hot(test)-spot temperature of beds is generally 200 DEG C~380 DEG C, preferably 220 DEG C~350 DEG C.Distillate volume space velocity is generally 0.1~4.0 h-1, preferably 0.1~1.0 h-1, most preferably 0.1~0.6 h-1.The consumption of optional hydrogen make-up is more than or equal to 1 with the mol ratio of hydrogen in gas feed and alkene, and be preferably defined calculating more than 1.3.
In the method for the present invention, olefin-containing dry gas is by after hydrogenation, olefin(e) centent is generally less than equal to 1 mol% in product；Oxygen content is generally less than equal to 1 mgm-3。
In the inventive method, the method that (1) is matched somebody with somebody to catalyst using level, the hydrogenation depth for walking reactions steps from surface to control this to react.I.e. along the direction of Flow of Goods and Materials, the hydrogenation activity of institute's loading catalyst is stepped up, and hydrogenation reaction depth is steadily stepped up along the direction of Flow of Goods and Materials, and reaction heat is also steadily progressively to release.(2) in olefin-containing dry gas reaction feed, if introducing one distillate simultaneously, the gas of former reaction will be caused（Dry gas）Gu-（Catalyst）Reaction, is converted into gas（Dry gas）- liquid（Distillate）Gu-（Catalyst）Reaction.At least partly it is at reaction conditions liquid due to introduced distillate, distillate charging forms trickle bed using dropwise addition state, i.e. distillate on beds, and forms one layer of oil film in catalyst surface.Oil film（Liquid film）Formation, increased the reactions steps of reaction mass transfer, that is, the mass transfer step of external diffusion is increased, so as to change original dry gas hydrogenation reaction course.The reaction mechanism mechanism of reaction after change is changed into following seven step：①、C2Alkene needs first to be diffused into this oil film；②、C2Alkene is through oil slick's pervasion to catalyst surface；③、C2Olefin adsorption is on hydrogenation sites；④、C2Alkene completes hydrogenation reaction；⑤、C2Alkane is desorbed from hydrogenation sites；⑥、C2Alkane is diffused into oil film from catalyst surface；⑦、C2Alkane is diffused into product from oil film.
Therefore, the inventive method has the advantages that compared with prior art：
1st, in C2When olefin component carries out hydrogenation reaction, due to the method that catalyst is matched somebody with somebody using level, realize the mass transfer step from reaction to control this to react.The hydrogenation activity of institute's loading catalyst is stepped up, and hydrogenation reaction depth is steadily stepped up along the direction of Flow of Goods and Materials, and reaction heat is also steadily progressively to release.Reaction result is：The relatively average reaction speed of beds entrance is reduced, the solely big problem of relatively average one section of the reaction speed of beds entrance is changed；Greatly reduce the difference of each section of phase average reaction speed of beds, the relatively average reaction speed of each section of beds is relatively more uniform.
2nd, in C2When olefin component carries out hydrogenation reaction, when one distillate is further introduced in charging, the presence of oil film is formed by this distillate so that hydrogenation surface reaction controlling step originally, changed into present --- limited diffusion-controlled step and surface reaction controlling step.Thus further slow down C2Olefin component hydrogenation reaction speed, i.e., the hydrogenation reaction speed of olefin-containing dry gas from it is original quickly, controlled very little, become for present controlled reaction.
3rd, after introducing one distillate, change original dry gas hydrogenation reaction course, reaction speed is controlled with this, be hydrogenated with saturation in the concentration of reactor inlet section so as to avoid alkene, it is to avoid hydrogenation reaction heat reactor inlet section the release of a large amount of concentrations, so as to the concentration for having delayed reaction heat is released, so that reaction bed temperature is than more uniform, reaction temperature rising has reduced, and " thermometer bulb " of beds is greatly gentle, and this result is also beneficial to extend the service life of catalyst.
4th, in the inventive method, it is only necessary to which minimal amount of distillate can form liquid film on beds, the requirement for changing the reaction mechanism mechanism of reaction and control reaction speed is met, therefore the consumption of distillate can be with fewer.
5th, because dry gas hydrogenation plant is typically each to build oil plant in, selectable distillate wider range, therefore the method for the present invention easily realizes, while also will not additionally increase production cost.
Specific embodiment
The method of the present invention is described in further detail below by specific embodiment.
Raw material used is shown in Table 2 in comparative example of the present invention and embodiment.The physical property of reaction catalyst used is shown in Table 3, and catalyst is needed to be vulcanized when in use, and vulcanisation operation is carried out using the vulcanization method of this area, is repeated no more.Reaction condition is shown in Table 5.
The dry gas raw material of table 2 is constituted, v%
Table
3
The physico-chemical property of catalyst.
Table
4
Distillate main character.
Comparative example
1
Reaction uses fixed bed reactors, using upper feeding mode.Four conversion zones are set in hydrogenation reactor, along Flow of Goods and Materials direction, isometric ratio filling.Using listed catalyst E in table 3, hydrogenating materials gas is the coking dry gas of Sinopec oil plant, and composition is shown in Table 2, reaction condition and the results are shown in Table 5.
From the reaction result in table 5, catalyst grading distribution scheme is provided without, and hydrogenation reaction is carried out only with single coking dry gas, reaction bed temperature rise is up to 110.4 DEG C, and hot(test)-spot temperature is higher；Average reaction temperature is 217.9 DEG C, is unfavorable for extending catalyst service life.
Table
5
Hydrogenation reactor operating condition and result
*, there is 5.83v% because the alkene in unstripped gas is total, and hydrogen content is only 7.71v%；So when hydrogenation reaction is carried out, hydrogen is covered preferably by 5% or so of dry gas inlet amount.
*, is along dry gas feedstock direction, different catalysts bed（Conversion zone）Temperature.Wherein, 1 is the first bed inlet temperatures, and 2,3,4,5 are respectively each beds medium temperature.
Embodiment
1
Reaction uses fixed bed reactors, upper feeding；Catalyst is using four sections of fillings, and filling ratio is with comparative example 1.From top to bottom, catalyst is followed successively by A, B, C, D.Its physical property is listed in table 3.Hydrogenating materials gas is coking dry gas, and composition is shown in Table 2.Reaction feed only includes coking dry gas, and does not include distillate.Reaction condition and the results are shown in Table 5.
From the reaction result in table 5, using catalyst grading distribution scheme of the present invention, and hydrogenation reaction is carried out only with single coking dry gas, reaction bed temperature rise is up to 61.2 DEG C.Compared with comparative example 1, hot(test)-spot temperature is greatly reduced；Average reaction temperature is 216.2 DEG C, is conducive to extending catalyst service life.
Embodiment 2
Reaction uses fixed bed reactors, upper feeding；Catalyst is using four sections of fillings, and filling ratio is with comparative example 1.From top to bottom, catalyst is followed successively by A, B, C, D.Its physical property is listed in table 3.Hydrogenating materials gas is coking dry gas, and composition is shown in Table 2.Reaction feed is in addition to coking dry gas, while there is refined naphtha, it feeds and coking dry gas parallel feeding.The main character of refined naphtha is shown in Table 4.Reaction condition and the results are shown in Table 5.
From the reaction result in table 5, after refining naphtha two improvements method using catalyst grading loading and introducing, reaction " thermometer bulb " is greatly reduced, and reaction temperature rising is reduced to 47.9 DEG C by original 110.4 DEG C；But average reaction temperature is 213.9 DEG C, and almost unchanged, reaction result is still qualified.
In addition, the relatively average reaction speed under comparative example 1, the reaction condition of embodiment 2 is listed in Table 6 below.
From data in table 6, when catalyst is only with type of feed in comparative example 1, the relatively average reaction speed difference between each section is larger；After refined naphtha of being gone forward side by side using grading loading, the difference of the relatively average reaction speed between each section is greatly reduced.
Table
6
The contrast of the relatively average reaction speed of each section of catalyst
Note：1st, self-defined one concept of relatively average reaction speed；The conversion ratio of conversion ratio/four section of relatively average reaction speed=certain section, is used to represent certain section of fast how many concept of the average response speed than another section.
2nd, it is 1 to set the 4th section of average response speed.
Embodiment
3
Reaction uses fixed bed reactors, upper feeding；Catalyst is using four sections of fillings, and filling ratio is with comparative example 1.From top to bottom, catalyst is followed successively by A, B, C and D, and its physical property is listed in table 3.Hydrogenating materials gas is coking dry gas, and composition is shown in Table 2.Reaction feed is in addition to coking dry gas, while also entering catalytic diesel oil, it feeds and coking dry gas parallel feeding.The main character of catalytic diesel oil is shown in Table 4.Reaction condition and the results are shown in Table 5.
From the reaction result in table 5, using catalyst grading loading and after introducing catalytic diesel oil two improvements method, it is also possible to reaction " thermometer bulb " is greatly reduced, reaction temperature rising is reduced to 45.5 DEG C by original 110 DEG C；Average reaction temperature is 213.4 DEG C, and almost unchanged, reaction result is still qualified.
Embodiment 4
Reaction uses fixed bed reactors, upper feeding；Catalyst is using four sections of fillings, and filling ratio is with comparative example 1.From top to bottom, catalyst is followed successively by A, B, C and D, and its physical property is listed in table 3.Hydrogenating materials gas is thermal cracking dry gas, and composition is shown in Table 2.Reaction feed is in addition to entering thermal cracking dry gas, while also entering one catalytic diesel oil, it feeds and thermal cracking dry gas parallel feeding.The main character of catalytic diesel oil is shown in Table 4.Reaction condition and the results are shown in Table 5.
From the reaction result in table 5, using catalyst grading loading and after introducing catalytic diesel oil two improvements method, it is also possible to reaction " thermometer bulb " is greatly reduced, reaction temperature rising is reduced to 48.4 DEG C by original 110 DEG C；Average reaction temperature is 216.1 DEG C, and almost unchanged, reaction result is still qualified.
Claims (21)
1. a kind of method of dry gas producing ethylene cracking material through hydrogenation, including herein below：
Dry gas containing alkene, optional hydrogen make-up, cocurrent enter fixed bed hydrogenation reactor, are contacted with hydrogenation catalyst under hydrogenation process conditions and are reacted, and gained product is by obtaining the dry gas of alkene saturation after separation；
Wherein include more than two conversion zones in hydrogenation reactor, according to the engagement sequence with material, the activity of hydrogenation catalyst is higher than the activity of hydrogenation catalyst in upstream reaction section in downstream reaction section, and the activity of wherein hydrogenation catalyst is represented with the height of contained active metal component content in catalyst.
2. in accordance with the method for claim 1, it is characterized in that, according to the engagement sequence with reaction mass, in terms of metal oxide, in downstream reaction section in hydrogenation catalyst active metal component content high 2~30 percentage of the content than active metal component in hydrogenation catalyst in adjacent upstream reaction section, 3~20 percentage preferably high.
3. according to the method described in claim 1 or 2, it is characterised in that described hydrogenation catalyst is load hydrogenation catalyst or body phase hydrogenation catalyst.
4. in accordance with the method for claim 3, it is characterised in that described load hydrogenation catalyst include carrier and load active metal component, active metal component with the content that oxide is counted be 5 wt%~35 wt%.
5. in accordance with the method for claim 4, it is characterised in that described carrier is porous refractory inorganic oxide or activated carbon, and described active metal component is selected from one or more in W, Mo, Ni and Co.
6. in accordance with the method for claim 3, it is characterised in that described body phase hydrogenation catalyst contains tri- kinds of metal components of Mo, W, Ni, wherein W, Ni exists with composite oxides form：NixWyOz, z=x+3y, Mo exist with oxide form：MoO3；Composite oxides NixWyOzThe mol ratio of middle x and y is 1: 8~8: 1, composite oxides NixWyOzWith oxide M oO3Weight ratio be 1: 10~10: 1；Composite oxides Ni in bulk phase catalystxWyOzWith oxide M oO3Gross weight content be 40%~100%.
7. in accordance with the method for claim 1, it is characterised in that the number of conversion zone is 3~5 in hydrogenation reactor, the volume of the hydrogenation catalyst of the interior filling of each conversion zone is equal or different.
8. in accordance with the method for claim 7, it is characterized in that, include 4 conversion zones in reactor, according to the engagement sequence with reaction mass, the weight content of first conversion zone, the second conversion zone, the 3rd conversion zone and the active metal component in the 4th conversion zone in hydrogenation catalyst in terms of oxide is respectively 5%~20%, 10%~25%, 15%~30%, 20%~50%.
9. in accordance with the method for claim 8, it is characterized in that, according to the engagement sequence with reaction mass, the weight content of the first conversion zone, the second conversion zone, the 3rd conversion zone and the active metal component in the 4th conversion zone in hydrogenation catalyst in terms of oxide is respectively 5%~20%, 10%~25%, 15%~30% and 20%~50%.
10. in accordance with the method for claim 1, it is characterised in that the volume fraction of alkene is more than 2.0v%, preferably 4.0v%~9.0v% in the described dry gas raw material containing alkene；Oxygen content is 100 mgm-3More than, preferably 300~1200
mg·m-3。
11. in accordance with the method for claim 1, it is characterised in that the described dry gas raw material containing alkene is selected from coking dry gas, catalytic cracked dry gas, thermal cracking dry gas, is hydrocracked one or more in rich gas or catalytic reforming gas.
12. in accordance with the method for claim 10, it is characterised in that contains hydrogen in the dry gas raw material of described olefin-containing simultaneously, the volume fraction of hydrogen is 2
More than v%.
13. in accordance with the method for claim 12, it is characterised in that the ratio between molar fraction of hydrogen and alkene is more than 1.0 in the dry gas of olefin-containing.
14. in accordance with the method for claim 1, it is characterised in that while olefin-containing dry gas feeds, and one distillate is introduced toward reactor is interior, and described distillate is at least partly at reaction conditions liquid.
15. in accordance with the method for claim 13, it is characterised in that the initial boiling point of described distillate is higher than 50 DEG C, and the end point of distillation is less than 400 DEG C.
16. in accordance with the method for claim 13, it is characterised in that described distillate not olefin-containing, the content of contained monoolefine is not higher than 4.0 wt%.
17. in accordance with the method for claim 13, it is characterised in that described distillate is selected from refined naphtha, non-aromatic gasoline, hydrofinishing aviation kerosine or hydrogenated diesel oil.
18. in accordance with the method for claim 1, it is characterised in that described hydrogenation process conditions include：Reaction pressure is 0.5~6.0 MPa, and reaction inlet temperature is 120 DEG C~300 DEG C, and reaction outlet temperature is 130 DEG C~400 DEG C, and the volume space velocity of olefin-containing dry gas is 100~10000 h-1。
19. in accordance with the method for claim 13, it is characterised in that the volume space velocity of the distillate is 0.1~4.0 h-1。
20. in accordance with the method for claim 18, it is characterised in that the volume space velocity of the distillate is 0.1~1.0 h-1。
21. in accordance with the method for claim 1, it is characterised in that the consumption of optional hydrogen make-up mol ratio of hydrogen and alkene in gas feed is defined calculating more than or equal to 1.
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|---|---|---|---|---|
| US4482767A (en) * | 1983-12-20 | 1984-11-13 | Uop Inc. | Process for production of alcohols and LPG |
| CN1075740A (en) * | 1992-10-27 | 1993-09-01 | 中国石油化工总公司 | Oil refinery dry gas and the charging of petroleum naphtha mixed phase are produced hydrogen, methane, carbon monoxide, the method for carbonic acid gas from hydrofining |
| CN102443430A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing ethylene cracking material by hydrogenising liquefied petroleum gas |
| CN103450941A (en) * | 2012-05-30 | 2013-12-18 | 中国石油化工股份有限公司 | Method for producing ethylene cracking raw material from coking dry gas |
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| US4482767A (en) * | 1983-12-20 | 1984-11-13 | Uop Inc. | Process for production of alcohols and LPG |
| CN1075740A (en) * | 1992-10-27 | 1993-09-01 | 中国石油化工总公司 | Oil refinery dry gas and the charging of petroleum naphtha mixed phase are produced hydrogen, methane, carbon monoxide, the method for carbonic acid gas from hydrofining |
| CN102443430A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing ethylene cracking material by hydrogenising liquefied petroleum gas |
| CN103450941A (en) * | 2012-05-30 | 2013-12-18 | 中国石油化工股份有限公司 | Method for producing ethylene cracking raw material from coking dry gas |
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| 宋金文: ""炼厂干气自氢加氢精制的工艺技术"", 《安庆石化》 * |
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